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Publication numberUS6020456 A
Publication typeGrant
Application numberUS 09/186,705
Publication dateFeb 1, 2000
Filing dateNov 6, 1998
Priority dateJul 14, 1997
Fee statusPaid
Also published asEP0892003A2, EP0892003A3, US5917005
Publication number09186705, 186705, US 6020456 A, US 6020456A, US-A-6020456, US6020456 A, US6020456A
InventorsDaniel Joseph Brunelle, Tina Lynn Grubb, Gordon Lee Tullos
Original AssigneeGeneral Electric Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Copolyetherimides with resistance to high temperatures
US 6020456 A
Abstract
Copolyetherimides are prepared by conventional means from hindered diamines such as the isomeric methyl-4,6-diethyl-1,3-phenylenediamines and bis(2-chloro-4-amino-3,5-diethylphenyl)methane. They have unusually high glass transition temperatures.
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Claims(8)
What is claimed is:
1. A copolyetherimide comprising structural units of the formulas ##STR7## wherein: Q is a divalent aliphatic or aromatic radical and A1 is a divalent radical of the formula ##STR8## A2 is m- or p-phenylene or a bis(alkylene)polydiorganosiloxane radical or has the formula ##STR9## X is O, S or NR4 ; R1 is an alkyl radical having from 2 to about 10 carbon atoms;
each R2 is independently C1-6 alkyl or halo;
R3 is C1-3 gem-alkylene;
R4 is hydrogen or C1-6 alkyl;
each of m, n and p is independently 0 or 1; and
z is 0 or 1.
2. The copolyetherimide according to claim 1 comprising about 10-90 mole percent of units of formula I.
3. The copolyetherimide according to claim 1 wherein A2 is m-phenylene or p-phenylene.
4. The copolyetherimide according to claim 3 wherein said units of formula I have the formula ##STR10## and said units of formula III have the formula ##STR11##
5. A copolyetherimide according to claim 1 wherein A1 has the formula wherein z is 0 or 1.
6. The copolyetherimide according to claim 5 wherein said units of formula I have the formula ##STR12## and said units of formula III have the formula ##STR13##
7. The copolyetherimide according to claim 1 wherein A1 has the formula
8. The copolyetherimide according to claim 7 wherein said units of formula I have the formula and said units of formula III have the formula ##STR14##
Description

This application is a division of application Ser. No. 08/893,596, filed Jul. 14, 1997, U.S. Pat. No. 5,917,005 which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

This invention relates to polyetherimides. More particularly, it relates to polyetherimides having extremely good resistance to high temperatures.

Polyetherimides are well known commercially available polymers having advantageous properties including thermal oxidative resistance, good mechanical strength, excellent electrical properties and good chemical resistance. Commercially available polyetherimides include those of the type which may be prepared by the reaction of such aromatic amines as m- and p-phenylenediamine with bis(ether anhydrides) such as 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, hereinafter sometimes designated "BPADA" for brevity. Their temperature stability is high, as shown by a glass transition temperature in the range of 215-220 C.

It is of interest, however, to prepare polyetherimides having still better resistance to high temperatures. Glass transition temperatures above 250 C. would be especially desirable.

SUMMARY OF THE INVENTION

The present invention provides a genus of polyetherimides having extremely good resistance to high temperatures. The glass transition temperatures of these new polymers typically range from about 250 C. to as high as 300 C.

In one of its aspects, the invention is directed to copolyetherimides comprising structural units of the formula

and ##STR1## wherein Q is a divalent aliphatic or aromatic radical and A1 is a divalent radical of the formula ##STR2## wherein R1 is an alkyl radical having from 2 to about 10 carbon atoms, each R2 is independently C1-6 alkyl or halo, R3 is C1-3 gem-alkylene 3 and each of m, n and p is independently 0 or 1;

and A2 is m- or p-phenylene or a bis(alkylene)polydiorganosiloxane radical or has the formula ##STR3## wherein X is O, S or NR4, z is 0 or 1 and R4 is hydrogen or C1-6 alkyl.

DETAILED DESCRIPTION; PREFERRED EMBODIMENTS

The preferred Q radical in the polyetherimides of this invention has the formula ##STR4## which may be considered as being derived from BPADA (preferably) or its 2,3-isomer.

The A1 radical has formula II in which each R1 value is an alkyl radical having from form 2 to about 10 and preferably 2-3 carbon atoms. Ethyl radicals are most preferred. The R2 values, when present, are C1-6 alkyl or halo, especially methyl or chloro. R3, when present, is a C1-3 gem-alkylene radical; that is, one in which both free valence bonds are attached to the same carbon atom. It is preferably methylene.

As will be apparent from formula II, the A1 radical may be monocyclic (m is 0) or bicyclic (m is 1). Further, the free valence bonds (or the single free valence bond and the bond connected to R3) may be in the para or meta positions.

The preferred A1 radicals are, first, the two isomeric structures in which m is 0, the R1 radicals are ethyl in the 4- and 6-positions, R2 is methyl in the 2- or 5-position, n is 1 and the free valence bonds are in the 1-and 3-positions, and second, the structure in which m and p are each 1, each R1 is ethyl in an ortho-position to the free valence bonds, R2 is chloro, R3 is methylene and the bonds connected to R3 are in the para positions from the free valence bonds.

These radicals correspond to the diamines having the respective formulas ##STR5## wherein z is 0 or 1, and ##STR6## Said diamines are respectively the two isomeric methyl-4,6-diethyl-1,3-phenylenediamines (singly or in admixture) and bis(2-chloro-4-amino-3,5-diethylphenyl)methane, which are respectively commercially available from Albemarle Corporation as "Ethacure 100" (mixture of isomers) and from Lonza Ltd. as "Lonzacure M-CDEA".

The polyetherimides of this invention include homopolyetherimides (consisting of units of formula I. They also include copolyetherimides, a preferred class of which comprises such units in combination with units of formula III, wherein A2 is a non-silicon-containing organic or bis(alkylene)polydiorganosiloxane radical or has formula IV. Suitable A2 radicals include aromatic and especially C6-20 aromatic radicals, as illustrated by m-phenylene, p-phenylene, bis(4-phenylene)methane and bis(4-phenylene) ether radicals, and aliphatic radicals, especially C2-20 aliphatic radicals such as ethylene, trimethylene, hexamethylene and neopentylene. The aromatic radicals are generally preferred, and especially the m-phenylene and p-phenylene radicals; i.e., those present in m-phenylenediamine and p-phenylenediamine.

The proportion of units of formula I in the co polyetherimides of this invention is preferably sufficient to produce a polyetherimide having a glass transition temperature of at least about 230 C. About 10-90 mole percent of units of formula I is typical, with about 40-60 mole percent often being preferred.

The polyetherimides of this invention may be prepared by conventional methods, conducted under art-recognized conditions. One generally applicable method is the reaction of at least one appropriate diamine with at least one tetracarboxylic acid or dianhydride or other functional derivative (e.g., tetrahalide) thereof. Preparation may also be by the reaction of at least one bisphenol salt, typically the disodium salt, with at least one appropriate bis(halo- or nitro phthalimide), most often in a solvent of low polarity and in the presence of a thermally stable phase transfer catalyst such as a hexaalkylguanidinium halide.

The preparation of the polyetherimides of this invention is illustrated by the following examples. Molecular weights are weight average and were determined by gel permeation chromatography.

EXAMPLE 1

Anhydrous bisphenol A disodium salt was prepared by the reaction of bisphenol A with an equimolar proportion of 50% aqueous sodium hydroxide solution followed by removal of water by azeotropic distillation in xylene.

"Ethacure 100" diamine (17.83 g, 100 mmol) was added in a nitrogen atmosphere to a solution of 36.51 g (200 mmol) of 4-chlorophthalic anhydride in 200 ml of o-dichlorobenzene at 135 C. The solution turned brown and then became colorless when the addition was complete. About 20 mg of 4-dimethylaminopyridine was added as a catalyst and the solution was heated at 165 C. for 1 hour and under reflux for 3 hours. High pressure liquid chromatographic analysis indicated disappearance of the reactants with formation of four isomeric products. The solution was concentrated to about 100 ml, cooled and poured into petroleum ether, affording the desired bis(chlorophthalimide) mixture in 85% yield.

A 50-ml 3-necked flask was oven dried, transferred to a nitrogen dry box and charged with 2.764 g (10.15 mmol) of anhydrous bisphenol A disodium salt and 5.074 g (10 mmol) of the above-prepared bis(chlorophthalimide) mixture. The flask was capped and fitted with a condenser, nitrogen introduction means and mechanical stirrer. o-Dichlorobenzene, 30 ml, was added and the mixture was heated to reflux and about 5 ml of solvent removed by distillation. Hexa-n-propylguanidinium chloride, 175 mg (0.5 mmol), was added over one minute in solution in about 1 ml of o-dichlorobenzene, whereupon a vigorous exothermic reaction occurred with dissolution of solids and thickening of the solution. The mixture was sampled and analyzed periodically. When molecular weight growth was complete, the reaction was quenched with acetic acid and cooled to room temperature.

The product solution was diluted with methylene chloride, washed with 3% aqueous hydrochloric acid solution and water several times and vacuum stripped to remove methylene chloride. The product polyetherimide was then isolated by precipitation into methanol and filtration. It had a weight average molecular weight of 137,500 and a glass transition temperature of 295 C. after a 15-minute reaction. The molecular weight after a 5-minute reaction was 112,000.

EXAMPLE 2

The procedure of Example 1 was repeated, substituting anisole for the o-dichlorobenzene as solvent. After reaction periods of 5, 15 and 30 minutes, the product polyetherimides had weight average molecular weights of 24,000, 81,000 and 112,000, respectively.

EXAMPLE 3

The procedure of Example 1 was repeated, using a mixture containing equimolar proportions of the mixed bis(chlorophthalimides) employed in Example 1 and the bis(chlorophthalimide) of m-phenylenediamine. After 5 and 15 minutes of reaction, the product copolyetherimides had weight average molecular weights of 85,000 and 102,000, respectively.

EXAMPLE 4

A round-bottomed flask equipped with a mechanical stirrer and a nitrogen purge line was charged with 10.238 g (19.671 mmol) of BPADA, 3.507 g (19.671 mmol) of "Ethacure 100" diamine and 44 ml of N-methylpyrrolidone. The mixture was stirred for 24 hours under nitrogen, after which 20 ml of xylene was added and the mixture was heated at 180 C. for 10 hours. The resulting polyetherimide was precipitated into methanol, filtered, washed with methanol and dried under vacuum. It had a molecular weight of 54,100.

EXAMPLE 5

The procedure of Example 4 was repeated, using a mixture containing equimolar proportions of "Ethacure 100" diamine and m-phenylenediamine. A corresponding copolyetherimide was obtained.

EXAMPLE 6

The procedure of Example 1 was repeated, substituting "Lonzacure M-CDEA" diamine for the "Ethacure 100" diamine on an equimolar basis. The resulting polyetherimide had a glass transition temperature of 252 C.

EXAMPLE 7

The procedure of Example 4 was repeated, substituting "Lonzacure M-CDEA" diamine for the "Ethacure 100" diamine on an equimolar basis. A similar product was obtained.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4550156 *Oct 26, 1984Oct 29, 1985General Electric CompanyPolyetherimide copolymers
US4680373 *May 27, 1986Jul 14, 1987General Electric CompanyProcess for the production of a random copolymer containing repeating polyimide units and repeating polyetherimide units
US5189115 *Nov 15, 1990Feb 23, 1993Amoco CorporationPolyetherimide copolymers
US5608013 *Mar 7, 1995Mar 4, 1997Hitachi Chemical Company, Ltd.Polyimides and thermosetting resin compositions containing the same
EP0336998A1 *May 18, 1988Oct 18, 1989E.I. Du Pont De Nemours And CompanyHighly soluble aromatic polyimides
Non-Patent Citations
Reference
1Ulery et al., "Highly Soluble Polyimides From Sterically Hindered Diamines," Polym. Prep., , 38, 182-3 (1997).
2 *Ulery et al., Highly Soluble Polyimides From Sterically Hindered Diamines, Polym. Prep., , 38, 182 3 (1997).
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6235866 *Oct 6, 1999May 22, 2001General Electric CompanySlurry preparation of bis (halophthalimides) and of polyether polymers
US6849706 *Aug 25, 2003Feb 1, 2005General Electric CompanyCopolyetherimides
US6919418 *Aug 25, 2003Jul 19, 2005Farid Fouad KhouriApproach to reduce cyclics formation in 3-CIPA based polyetherimide polymers
US6919422 *Sep 22, 2003Jul 19, 2005General Electric CompanyPolyimide resin with reduced mold deposit
US7074882 *Jul 2, 2004Jul 11, 2006Nitto Denko CorporationPolyimide resin for electrical insulating material
US7714095Feb 28, 2006May 11, 2010Sabic Innovative Plastics Ip B.V.Phase transfer catalyzed method for preparation of polyetherimides
US8524854 *Dec 28, 2010Sep 3, 2013Sabic Innovative Plastics Ip B.V.Chloro-substituted polyetherimides having improved relative thermal index
US8907042Oct 28, 2011Dec 9, 2014Sabic Global Technologies B.V.Polyetherimides, methods of manufacture, and articles formed therefrom
US8945694Mar 19, 2007Feb 3, 2015Sabic Global Technologies B.V.Poly aryl ether ketone polymer blends
US9006348Sep 16, 2005Apr 14, 2015Sabic Global Technologies B.V.Poly aryl ether ketone polymer blends
US20110263791 *Dec 28, 2010Oct 27, 2011Sabic Innovative Plastics Ip B.V.Chloro-substituted polyetherimides having improved relative thermal index
US20140171613 *Dec 18, 2012Jun 19, 2014Sabic Innovative Plastics Ip B.V.Process for the production of polyetherimides
WO2005021618A2 *Aug 10, 2004Mar 10, 2005Gen ElectricPhase transfer catalyzed method for preparation of polyetehrimides
WO2007035402A2Sep 14, 2006Mar 29, 2007Gen ElectricImproved poly aryl ether ketone polymer blends
Classifications
U.S. Classification528/353, 528/350, 525/436
International ClassificationC08G73/10
Cooperative ClassificationC08G73/105, C08G73/1064, C08G73/1042, C08G73/106
European ClassificationC08G73/10L1, C08G73/10K, C08G73/10M2, C08G73/10M1
Legal Events
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Mar 17, 2014ASAssignment
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS
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Nov 7, 2000CCCertificate of correction